CN109755471B - Lithium iron oxide-based lithium battery negative electrode material and preparation method and application thereof - Google Patents
Lithium iron oxide-based lithium battery negative electrode material and preparation method and application thereof Download PDFInfo
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- CN109755471B CN109755471B CN201910043278.XA CN201910043278A CN109755471B CN 109755471 B CN109755471 B CN 109755471B CN 201910043278 A CN201910043278 A CN 201910043278A CN 109755471 B CN109755471 B CN 109755471B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 55
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 27
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 22
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000006232 furnace black Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 30
- 230000008569 process Effects 0.000 description 11
- 239000013543 active substance Substances 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 229910013695 LiCl—SrCl2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种基于铁酸锂的锂电池负极材料及其制备方法和应用，属于锂离子电池电极材料的制备及应用领域。该基于铁酸锂的锂电池负极材料，包括铁酸锂，所述的铁酸锂的化学式为Li2Fe3O5，其形貌为八面体结构颗粒，粒径为0.2～10μm。还包括导电碳、粘结剂和溶剂。其制备方法为：将各个物质混合后，搅拌得到。用该负极材料可以制备锂电池。本方法以八面体结构的铁酸锂材料为基础制备的锂离子负极材料，不仅提高了导电性，而且缓解了锂离子在嵌入和脱出的过程中巨大的体积变化，提髙了锂离子负极材料的电化学稳定性，可以极大的改进石墨作为传统锂离子电池负极材料的较低的理论比容量，解决了锂离子电池较低比容量这一发展障碍。
A lithium battery negative electrode material based on lithium ferrite and a preparation method and application thereof belong to the field of preparation and application of lithium ion battery electrode materials. The lithium ferrite-based lithium battery negative electrode material includes lithium ferrite, the chemical formula of the lithium ferrite is Li 2 Fe 3 O 5 , the morphology is octahedral structure particles, and the particle size is 0.2-10 μm. Also includes conductive carbon, binder and solvent. The preparation method is as follows: after mixing each substance, stirring is obtained. Lithium batteries can be prepared with the negative electrode material. The lithium ion anode material prepared by the method based on the lithium ferrite material with octahedral structure not only improves the conductivity, but also alleviates the huge volume change during the insertion and extraction of lithium ions, and improves the lithium ion anode material. The electrochemical stability of graphite can greatly improve the low theoretical specific capacity of graphite as a negative electrode material for traditional lithium-ion batteries, and solve the development obstacle of low specific capacity of lithium-ion batteries.
Description
Technical Field
The invention belongs to the field of preparation and application of electrode materials of lithium ion batteries, and particularly relates to a lithium iron-based negative electrode material of a lithium battery, and a preparation method and application thereof.
Background
The lithium battery is used as a common energy storage device with wide market prospect and rapid development due to higher working voltage and specific energy, rapid charge and discharge, higher safety performance and the like, and has very wide application in daily life and production. How to improve the capacity and stability of the lithium battery is an important problem to be solved urgently.
The negative electrode material is used as a lithium ion acceptor, and has the characteristics of good structure, good chemical stability, high electronic conductivity and lithium ion conductivity in the lithium deintercalation process, and low cost and environmental friendliness. Most of the anode materials in commercial use are carbon-based materials, but the carbon-based materials have many disadvantages and shortcomings, and thus, some new non-carbon anode materials are receiving more and more attention from researchers.The non-carbon cathode material mainly focuses on some electrochemically active metals and metal oxides, such as tin (Sn), silicon (Si) and SnO2、Co3O4、Fe2O3And Fe3O4And the like. The capacity of the transition metal oxide material is multiplied compared with that of a carbon-based material, and the transition metal oxide material is more beneficial to development of a future high-specific-capacity lithium ion battery. The transition metal oxide negative electrode material with special morphology (nano hollow structure, mesoporous structure and three-dimensional nano structure) can be prepared by common physical or chemical methods such as a water/solvent thermal method, a sol-gel method, a metal precursor pyrolysis method, mechanical ball milling and the like. The cathode materials with special micro-morphology show good cycle stability and higher reversible capacity, and reduce the problems of volume change and particle agglomeration of the transition metal oxide cathode materials in the lithium intercalation and deintercalation cycle process to a certain extent. Meanwhile, another class of transition metal oxide composite negative electrode materials is also widely concerned and developed, and mainly comprises metal oxide/carbon composite nano materials, metal oxide/graphene composite materials, composite films and the like.
Fe3O4Is one of the potential negative electrode materials, and has high specific capacity (926mAh/g) and good electronic conductivity (2 × 10 ═ sigma)4S/m), low price and easy obtaining, abundant resources, no toxicity, environmental friendliness and the like, is superior to other transition metal oxides, and researches on nano ferroferric oxide with various shapes are successively reported. However, Fe3O4As a negative electrode material, the lithium intercalation and deintercalation process can generate obvious volume change and serious particle agglomeration and particle pulverization, which cause charge and Li+Poor transmission and diffusion performance, poor cycle stability, low rate performance and low first coulombic efficiency. How to find a new lithium ion battery cathode material, and the preparation method thereof needs to be a green preparation process with simple steps and low cost, so that the problems and difficulties can be overcome, and the lithium ion battery cathode material has macroscopic structural stability and microscopic excellent electrochemical performance and is a key problem to be solved by the current content.
Disclosure of Invention
The lithium iron based lithium battery cathode material is based on an octahedral structure based lithium iron material, and is applied to a lithium ion battery cathode material after being compounded with carbon. The lithium ion negative electrode material prepared on the basis of the lithium ferrite material with the octahedral structure not only improves the conductivity, but also relieves the huge volume change of lithium ions in the process of embedding and releasing, improves the electrochemical stability of the lithium ion negative electrode material, can greatly improve the lower theoretical specific capacity of graphite serving as the negative electrode material of the traditional lithium ion battery, and solves the development obstacle of the lower specific capacity of the lithium ion battery. The method is expected to provide technical support for the commercial application of the high-specific-capacity lithium ion battery cathode material in the future.
The lithium iron battery negative electrode material comprises lithium iron oxide, wherein the chemical formula of the lithium iron oxide is Li2Fe3O5The particle is octahedral particle with particle size of 0.2-10 μm.
The lithium iron oxide-based lithium battery negative electrode material further comprises conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon (8-2): 1, the adding mass of the binder accounts for 5-20% of the total mass of the lithium ferrite and the conductive carbon, and the binder comprises the following components in percentage by mass: solid matter (4-12): 1.
the solid matter is lithium ferrate and conductive carbon.
The conductive carbon is one or a mixture of acetylene black, conductive graphite, nano graphite, furnace black, Ketjen carbon black and carbon nano tubes.
The binder is one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, butyl rubber, sodium carboxymethylcellulose, polyacrylic acid and polyimide.
The solvent is one or a mixture of N-methyl pyrrolidone, dimethylformamide, tetrahydrofuran, carbon tetrachloride, water and ethanol.
The invention relates to a preparation method of a lithium iron oxide-based lithium battery negative electrode material, which comprises the following steps of:
step I:
weighing lithium ferrite, conductive carbon and a binder according to the proportion, and mixing and grinding to obtain a mixture;
step II:
and adding a solvent into the mixture, and uniformly stirring the mixture into paste to obtain the lithium iron oxide-based lithium battery negative electrode material.
In the step I, the lithium ferrite and the preparation method thereof comprise the following steps:
under the protection atmosphere of molten salt containing water vapor, taking iron oxide powder or pressed and sintered iron oxide sheets as a working cathode, taking graphite as a working anode, taking LiCl and a mixture of the LiCl and alkali metal chloride and/or alkaline earth metal chloride as Li molten salt electrolyte, and electrolyzing at 300-1000 ℃ and constant voltage of 0.7-1V to obtain a product lithium ferrite; in the molten salt protective atmosphere, the volume percentage of water vapor is 0.1-100 Vol.%, and the balance is argon gas;
in the preparation method of lithium ferrite, the Li molten salt electrolyte is LiCl or LiCl and NaCl, KCl, RbCl, CsCl, CaCl2、SrCl2、BaCl2、ZnCl2One or a mixture of several of them.
In the preparation method of the lithium ferrite, the electrolysis time is 10-120 min.
In the step II, the mixture is stirred uniformly for 10 hours.
The application of the lithium iron oxide-based negative electrode material of the lithium battery can be applied to the negative electrode material of the lithium ion battery.
An electrode plate comprises the lithium iron oxide-based lithium battery negative electrode material.
The method for preparing the electrode plate by adopting the lithium iron based lithium battery cathode material comprises the following steps:
step 1: coated current collector
Uniformly coating a lithium iron based lithium battery negative electrode material on a current collector, and performing vacuum drying at 70-90 ℃ for 12-20 h to obtain a pole piece; wherein the loading capacity of the active substance per unit area on the current collector is 0.8-5 mg;
step 2: calendering treatment
And rolling and cutting the pole piece to obtain the electrode pole piece.
In the step 1, the current collector is a copper foil or a carbon-coated copper foil.
The electrode plate is prepared by adopting the method for preparing the electrode plate.
The lithium ion battery adopts the electrode pole piece as a working electrode.
The method for preparing the lithium ion battery by adopting the electrode pole piece comprises the following steps:
and assembling the electrode plate, the diaphragm and the lithium plate into the lithium ion battery under the argon environment.
The lithium ion battery has the first discharge capacity of 900-1300mAhg at the rate of 200mA/g-1First reversible charge capacity of 750-950mAhg-1So that the first coulombic efficiency reaches 60-80%, and the reversible discharge specific capacity after 300 cycles is 500-800mAhg-1The coulombic efficiency is 95-100%.
Compared with the existing lithium ion battery cathode material based on ferroferric oxide, the lithium iron oxide-based lithium battery cathode material and the preparation method and the application thereof have the following advantages and beneficial effects:
1. the invention fully utilizes the good electric and heat conducting capacity and wide electrochemical window of the high-temperature molten salt, and can realize the regulation and control of the morphology and the granularity of the electrolysis product lithium iron oxide under the lower cathode polarization potential and the electrolysis temperature, thereby laying a foundation for the preparation of a high-specific-capacity cathode material.
2. The lithium ferrite-based lithium battery cathode material has special appearance and composition, and the preparation method of the lithium ferrite carries out electrolysis in high-temperature molten salt in a humid atmosphere, has lower energy consumption and shorter flow, and obviously improves the production efficiency. In addition, the lithium ferrite of the invention has uniform phase, and the preparation method thereof has no other by-products, thereby really realizing a short-flow novel process route for directly preparing the precursor of the lithium ion battery cathode material.
3. The high-specific-capacity lithium ferrite/carbon composite material applied to the lithium ion battery cathode material prepared by the invention has excellent long-cycle stability and rate capability.
Drawings
FIG. 1 is an XRD pattern in which (a) is iron oxide (Fe) as a raw material2O3) XRD pattern of (a); (b) XRD pattern of electrolytic product lithium ferrate.
Fig. 2 is an SEM image of lithium ferrate in the lithium-iron-based lithium battery negative electrode material of the present invention.
Fig. 3 is a charge-discharge graph of a battery prepared from a lithium iron oxide-based negative electrode material for a lithium battery.
Fig. 4 is a graph of the cycling performance of a battery made from a lithium iron oxide based negative electrode material for a lithium battery.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples, unless otherwise specified, the starting materials and equipment used are commercially available and the purity of the starting materials is analytical.
Example 1
In a lithium ferrite-based lithium battery cathode material, a preparation method of lithium ferrite comprises the following steps:
directly using iron oxide (Fe)2O3) The powder (XRD diagram shown in figure 1(a)) is used as a working cathode, graphite is used as a working anode, wherein the electrolyte is LiCl, the electrolysis temperature is 660 ℃, the electrolysis voltage is 1V, the electrolysis time is 60min, and the heating rate before electrolysis and the cooling rate after electrolysis are both 3 ℃/min. In the electrolysis process, the flow of argon introduced into the electrolysis cell is 600mL/min, the electrolysis cell is connected with a U-shaped quartz tube, deionized water is contained in the U-shaped quartz tube, after the argon flows through the U-shaped quartz tube, moist argon flows into a sealed reactor, and electrolysis is carried out under the protective atmosphere of fused salt containing water vapor. After the electrolysis experiment is finished, the cathode is lifted away from the molten saltAnd washing a large amount of deionized water to remove molten salt attached to the cathode, and drying to obtain an electrolysis product lithium iron oxide.
XRD and SEM test analysis are carried out on the prepared lithium ferrite, the XRD pattern of the lithium ferrite is shown in figure 1(b), the lithium ferrite is used for a precursor of a lithium battery negative electrode material, and the XRD pattern in figure 1 is analyzed to obtain the lithium ferrite prepared by the embodiment, the chemical formula of which is Li2Fe3O5。
The SEM image of lithium ferrate prepared in this example is shown in fig. 2, and from fig. 2, it can be seen that it is shaped as octahedral particles with an average particle size of 2 μm.
A lithium iron based lithium battery cathode material comprises the prepared lithium iron, conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon 2: 1, the adding mass of the binder accounts for 11.1 percent of the total mass of the lithium ferrite and the conductive carbon, and the solvent comprises the following components in percentage by mass: solid matter 9: 1.
the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the solvent is N-methyl pyrrolidone.
A preparation method of a lithium iron oxide-based lithium battery negative electrode material comprises the following steps:
weighing 6g of lithium ferrite, 3g of conductive carbon and 1g of binder, mixing and grinding, adding 80ml of N-methyl pyrrolidone, and magnetically stirring for 10 hours to form paste, thereby obtaining the lithium-iron-based lithium battery negative electrode material.
The process of assembling the button type half cell by the lithium iron oxide-based lithium battery cathode material comprises the following steps: coating the prepared lithium ferrite-based lithium battery negative electrode material on copper foil, and performing vacuum drying at 80 ℃ for 18h to prepare an electrode plate, wherein the loading amount of active substances in unit area on a current collector is 2 mg;
and slicing and tabletting the electrode slice, and then taking the electrode slice and a lithium slice as a counter electrode to assemble the CR2025 type button cell in a glove box. The assembled CR2025 type button cell is subjected to constant current charge and discharge test, the cycle stability and the rate performance of the assembled CR2025 type button cell are examined, and a charge and discharge curve chart is shown in figure 3. As can be seen from FIG. 3, the first discharge curve has two distinct regions, one at 0.8VThe long voltage plateau and subsequent voltage drop to 0.01V, which is mainly due to SEI film formation and Fe3+/Fe2+To Fe0A transition of (a); the second and third discharge curves substantially coincide.
The first discharge capacity, the first coulombic efficiency and the reversible charge capacity of the button cell prepared from the lithium iron oxide-based lithium battery negative electrode material of the embodiment are measured at room temperature, the cycle performance diagram is shown in fig. 4, and the results are as follows:
the first discharge capacity was 1102.7mAhg at a rate of 200mA/g-1First reversible charge capacity of 808.4mAhg-1Therefore, the first coulombic efficiency reaches 73.32 percent, and the reversible discharge specific capacity after 220 cycles is 604mAhg-1Coulombic efficiency was 100%.
Example 2
In a lithium ferrite-based lithium battery cathode material, a preparation method of lithium ferrite comprises the following steps: the difference from example 1 is that:
(1) pressing the iron oxide powder (20MPa, maintaining the pressure for 10 minutes), and sintering at the constant temperature of 800 ℃ for 2 hours to obtain a sheet cathode;
(2) the electrolytic voltage is 0.7V, the electrolytic time is 120min, and the electrolytic temperature is 450 ℃;
(3) the chemical component of the electrolyte is LiCl-KCl (wherein LiCl accounts for 59.2 mol%, and KCl accounts for 40.8 mol%);
a lithium iron based lithium battery cathode material comprises the prepared lithium iron, conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon 2: 1, the adding mass of the binder accounts for 11.1 percent of the total mass of the lithium ferrite and the conductive carbon, and the solvent comprises the following components in percentage by mass: solid matter 9: 1.
the conductive agent is conductive graphite, the binder is sodium carboxymethylcellulose, the solvent is a mixture of water and ethanol, the volume percentage of the ethanol is 95%, and the balance is water.
A preparation method of a lithium iron oxide-based lithium battery negative electrode material comprises the following steps:
6g of lithium ferrite prepared in the embodiment, 3g of conductive carbon and 1g of binder are weighed, mixed and ground, 80mL of solvent is added, and the mixture is magnetically stirred for 10 hours to form paste, so that the lithium battery negative electrode material based on the lithium ferrite is obtained.
The process of assembling the button type half cell by the lithium iron oxide-based lithium battery cathode material comprises the following steps: coating the prepared lithium ferrite-based negative electrode material of the lithium battery on copper foil, and performing vacuum drying at 70 ℃ for 20 hours to prepare an electrode plate, wherein the loading amount of active substances in unit area on a current collector is 0.8 mg;
and slicing and tabletting the electrode slice, and then taking the electrode slice and a lithium slice as a counter electrode to assemble the CR2025 type button cell in a glove box. Electrochemical performance tests were performed on a constant current charge and discharge system at a rate of 200 mA/g.
Example 3
The method is the same as example 1, except that:
(1) the electrolytic voltage is 0.9V, the electrolytic time is 20min, and the electrolytic temperature is 590 ℃;
(2) the chemical component of the electrolyte is LiCl-SrCl2(64.3:35.7mol％)；
(3) 6g of lithium ferrate prepared under the conditions, 3g of conductive carbon and 1g of binder were weighed, mixed and ground, 80ml of LN-methylpyrrolidone was added, and magnetic stirring was carried out for 10 hours. Coating the prepared slurry on copper foil to prepare an electrode plate, slicing and tabletting the electrode plate and a lithium sheet serving as a counter electrode, and assembling the CR2025 button cell in a glove box. Electrochemical performance tests were performed on a constant current charge and discharge system at a rate of 200 mA/g.
Example 4
In a lithium ferrite-based lithium battery cathode material, a preparation method of lithium ferrite comprises the following steps: the difference from example 1 is that:
(1) the electrolytic voltage is 0.8V, the electrolytic time is 90min, and the electrolytic temperature is 400 ℃;
(2) the electrolyte chemical composition is a mixture of LiCl-KCl-CsCl; (wherein, in terms of mole percent, LiCl: KCl: CsCl: 57.5:24.6:17.9 mol%);
a lithium iron based lithium battery cathode material comprises the prepared lithium iron, conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon 2: 1, the adding mass of the binder accounts for 11.1 percent of the total mass of the lithium ferrite and the conductive carbon, and the solvent comprises the following components in percentage by mass: solid matter 9: 1.
the conductive agent is conductive graphite, the binder is sodium carboxymethylcellulose, the solvent is a mixture of water and ethanol, the volume percentage of the ethanol is 95%, and the balance is water.
A preparation method of a lithium iron oxide-based lithium battery negative electrode material comprises the following steps:
6g of lithium ferrite prepared in the embodiment, 3g of conductive carbon and 1g of binder are weighed, mixed and ground, 80mL of solvent is added, and the mixture is magnetically stirred for 10 hours to form paste, so that the lithium battery negative electrode material based on the lithium ferrite is obtained.
The process of assembling the button type half cell by the lithium iron oxide-based lithium battery cathode material comprises the following steps: coating the prepared lithium ferrite-based lithium battery negative electrode material on copper foil, and performing vacuum drying at 90 ℃ for 12 hours to prepare an electrode plate, wherein the load of active substances in unit area on a current collector is 5 mg;
and slicing and tabletting the electrode slice, and then taking the electrode slice and a lithium slice as a counter electrode to assemble the CR2025 type button cell in a glove box. Electrochemical performance tests were performed on a constant current charge and discharge system at a rate of 200 mA/g.
Example 5
In a lithium ferrite-based lithium battery cathode material, a preparation method of lithium ferrite comprises the following steps: the same as in example 1.
A lithium iron based lithium battery cathode material comprises the prepared lithium iron, conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon 8: 1, the adding mass of the binder accounts for 20% of the total mass of the lithium ferrite and the conductive carbon, and the mass ratio of the binder to the conductive carbon is as follows: solid matter 4: 1.
the conductive agent is a mixture of nano graphite and carbon nano tubes (the mass ratio is 1:1), the binder is polyvinylidene fluoride and polytetrafluoroethylene (the mass ratio is 1:1), and the solvent is tetrahydrofuran.
A preparation method of a lithium iron oxide-based lithium battery negative electrode material comprises the following steps:
8g of lithium ferrite prepared in the embodiment, 1g of conductive carbon and 1.8g of binder are weighed, mixed and ground, 32mL of tetrahydrofuran is added, and the mixture is magnetically stirred for 10 hours to form paste, so that the lithium battery negative electrode material based on the lithium ferrite is obtained.
The process of assembling the button type half cell by the lithium iron oxide-based lithium battery cathode material comprises the following steps: coating the prepared lithium ferrite-based negative electrode material of the lithium battery on copper foil, and performing vacuum drying at 70 ℃ for 20 hours to prepare an electrode plate, wherein the loading amount of active substances in unit area on a current collector is 0.8 mg;
and slicing and tabletting the electrode slice, and then taking the electrode slice and a lithium slice as a counter electrode to assemble the CR2025 type button cell in a glove box. Electrochemical performance tests were performed on a constant current charge and discharge system at a rate of 200 mA/g.
Example 6
In a lithium ferrite-based lithium battery cathode material, a preparation method of lithium ferrite comprises the following steps: the same as in example 1.
A lithium iron based lithium battery cathode material comprises the prepared lithium iron, conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon 6:1, the adding mass of the binder accounts for 5% of the total mass of the lithium ferrite and the conductive carbon, and the binder comprises the following components in percentage by mass: solid matter 12: 1.
the conductive agent is furnace black and Ketjen carbon black (the mass ratio is 1:1), the binder is polyacrylic acid and polyimide (the mass ratio is 1:1), and the solvent is N-methylpyrrolidone.
A preparation method of a lithium iron oxide-based lithium battery negative electrode material comprises the following steps:
6g of lithium ferrite prepared in the embodiment, 3g of conductive carbon and 0.35g of binder are weighed, mixed and ground, 134ml of N-methyl pyrrolidone is added, and the mixture is magnetically stirred for 8 hours to form paste, so that the lithium battery negative electrode material based on the lithium ferrite is obtained.
The process of assembling the button type half cell by the lithium iron oxide-based lithium battery cathode material comprises the following steps: coating the prepared lithium ferrite-based lithium battery negative electrode material on copper foil, and performing vacuum drying at 80 ℃ for 14 hours to prepare an electrode plate, wherein the load of active substances in unit area on a current collector is 3 mg;
and slicing and tabletting the electrode slice, and then taking the electrode slice and a lithium slice as a counter electrode to assemble the CR2025 type button cell in a glove box. Electrochemical performance tests were performed on a constant current charge and discharge system at a rate of 200 mA/g.
Claims (14)
1. The lithium iron based lithium battery negative electrode material is characterized by comprising lithium iron, wherein the chemical formula of the lithium iron is Li2Fe3O5The shape of the particle is octahedral structure particle, and the particle size is 0.2-10 mu m;
the lithium iron oxide-based lithium battery negative electrode material further comprises conductive carbon, a binder and a solvent; wherein, according to the mass ratio, the lithium ferrite: conductive carbon (8-2): 1, the adding mass of the binder accounts for 5-20% of the total mass of the lithium ferrite and the conductive carbon, and the binder comprises the following components in percentage by mass: solid matter (4-12): 1; the solid matter is lithium ferrate and conductive carbon.
2. The lithium iron oxide-based negative electrode material for lithium batteries according to claim 1, wherein the conductive carbon is one or a mixture of acetylene black, conductive graphite, nano-graphite, furnace black, Ketjen carbon black and carbon nanotubes.
3. The lithium ferrite-based negative electrode material for a lithium battery as claimed in claim 1, wherein the binder is one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, butyl rubber, sodium carboxymethylcellulose, polyacrylic acid and polyimide.
4. The lithium iron oxide-based negative electrode material for lithium batteries according to claim 1, wherein the solvent is one or a mixture of N-methyl pyrrolidone, dimethylformamide, tetrahydrofuran, carbon tetrachloride, water and ethanol.
5. The method for preparing the lithium iron oxide-based lithium battery negative electrode material according to any one of claims 1 to 4, characterized by comprising the steps of:
step I:
weighing lithium ferrite, conductive carbon and a binder according to the proportion, and mixing and grinding to obtain a mixture;
step II:
and adding a solvent into the mixture, and uniformly stirring the mixture into paste to obtain the lithium iron oxide-based lithium battery negative electrode material.
6. The method for preparing a negative electrode material for a lithium ferrite-based lithium battery according to claim 5, wherein the lithium ferrite prepared in the step I comprises the following steps:
under the protection atmosphere of molten salt containing water vapor, taking iron oxide powder or pressed and sintered iron oxide sheets as a working cathode, taking graphite as a working anode, taking LiCl and a mixture of the LiCl and alkali metal chloride and/or alkaline earth metal chloride as Li molten salt electrolyte, and electrolyzing at 300-1000 ℃ and constant voltage of 0.7-1V to obtain a product lithium ferrite; in the molten salt protective atmosphere, the volume percentage of water vapor is 0.1-100 Vol.%, and the balance is argon.
7. The method of claim 6, wherein the Li fused salt electrolyte is LiCl or LiCl and NaCl, KCl, RbCl, CsCl, CaCl, or the like, in the method of preparing lithium ferrite2、SrCl2、BaCl2、ZnCl2One or a mixture of several of them.
8. The method for preparing a lithium ferrite-based negative electrode material for a lithium battery as claimed in claim 6, wherein the electrolysis time is 10 to 120min in the method for preparing lithium ferrite.
9. An electrode sheet, characterized by comprising the lithium iron oxide-based negative electrode material for lithium batteries according to any one of claims 1 to 4.
10. The method for preparing the electrode plate by adopting the lithium iron oxide-based lithium battery negative electrode material as claimed in any one of claims 1 to 4 is characterized by comprising the following steps:
step 1: coated current collector
Uniformly coating a lithium iron based lithium battery negative electrode material on a current collector, and performing vacuum drying at 70-90 ℃ for 12-20 h to obtain a pole piece;
step 2: calendering treatment
And rolling and cutting the pole piece to obtain the electrode pole piece.
11. The method for preparing an electrode plate according to claim 10, wherein in the step 1, the current collector is a copper foil or a carbon-coated copper foil.
12. A lithium ion battery, characterized in that the electrode sheet of claim 9 is used as a working electrode.
13. The method for preparing the lithium ion battery by adopting the electrode plate of claim 9 is characterized by comprising the following steps:
and assembling the electrode plate, the diaphragm and the lithium plate into the lithium ion battery under the argon environment.
14. The lithium ion battery of claim 12, wherein the lithium ion battery has a first discharge capacity of 900--1First reversible charge capacity of 750-950mAhg-1So that the first coulombic efficiency reaches 60-80%, and the reversible discharge specific capacity after 300 cycles is 500-800mAhg-1The coulombic efficiency is 95-100%.
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| CN105206779A (en) * | 2014-06-23 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Ceramic diaphragm and preparation method thereof |
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| CN105206779A (en) * | 2014-06-23 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Ceramic diaphragm and preparation method thereof |
| JP2017168255A (en) * | 2016-03-15 | 2017-09-21 | 株式会社東芝 | Nonaqueous electrolyte secondary battery, battery pack, and vehicle |
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